Methods and apparatus for in-situ cleaning of copper surfaces and deposition and removal of self-assembled monolayers

ABSTRACT

A method of processing includes: providing a substrate having a contaminant material disposed on the copper surface to a substrate support within a hot wire chemical vapor deposition (HWCVD) chamber; providing hydrogen (H 2 ) gas to the HWCVD chamber; heating one or more filaments disposed in the HWCVD chamber to a temperature sufficient to dissociate the hydrogen (H 2 ) gas; exposing the substrate to the dissociated hydrogen (H 2 ) gas to remove at least some of the contaminant material from the copper surface; cooling the one or more filaments to room temperature; exposing the substrate in the HWCVD chamber to one or more chemical precursors to deposit a self-assembled monolayer atop the copper surface; and depositing a second layer atop the substrate.

FIELD

Embodiments of the present disclosure generally relate to in-situcleaning of copper surfaces and deposition and removal of self-assembledmonolayers.

BACKGROUND

In the semiconductor industry, the main challenge in dealing with thesurfaces of copper (Cu) substrates is such surfaces when exposed to theenvironment, even to a clean room environment, form a thin surface oxidelayer, for example a thin surface layer containing Cu(OH)₂, CuO, Cu₂O,and CuCO₃. Proper cleaning of the copper surface is needed to properlydeposit other layers in a device stack. Typical methods of cleaning theoxidized Cu surfaces include a wet chemical clean, plasma cleaning, oran ozone treatment. However, the inventors have observed that wetcleaning processes can undesirably contaminate the copper surface due tothe usage of various acids and other chemicals. A plasma based cleaningprocess undesirably can damage the copper surface, especially when athin layer of copper, for example about 25 nm to about 50 nm, istreated.

Accordingly, the inventors have developed improved methods and apparatusfor in-situ cleaning of copper surfaces and deposition and removal ofself-assembled monolayers.

SUMMARY

Methods and apparatus for in-situ cleaning of copper surfaces anddeposition and removal of self-assembled monolayers are provided herein.In some embodiments, a method of processing a substrate having anexposed copper surface includes (a) providing a substrate having acontaminant material disposed on the copper surface to a substratesupport within a hot wire chemical vapor deposition (HWCVD) chamber; (b)providing hydrogen (H₂) gas to the HWCVD chamber; (c) heating one ormore filaments disposed in the HWCVD chamber to a temperature sufficientto dissociate the hydrogen (H₂) gas; (d) exposing the substrate to thedissociated hydrogen (H₂) gas to remove at least some of the contaminantmaterial from the copper surface; (e) cooling the one or more filamentsto room temperature; (f) exposing the substrate in the HWCVD chamber toone or more chemical precursors to deposit a self-assembled monolayeratop the copper surface; and (g) depositing a second layer atop thesubstrate.

In some embodiments, method of processing a substrate having an exposedcopper surface includes: providing a substrate having a contaminantmaterial disposed on the copper surface to a substrate support within ahot wire chemical vapor deposition (HWCVD) chamber; providing hydrogen(H2) gas to the HWCVD chamber; heating one or more filaments disposed inthe HWCVD chamber to a temperature of about 1000 to about 2400 degreesCelsius to dissociate the hydrogen (H₂) gas and heating the substratesupport to a temperature of about 50 to about 400 degrees Celsius;exposing the substrate to the dissociated hydrogen (H₂) gas to remove atleast some of the contaminant material from the copper surface; coolingthe one or more filaments to room temperature; heating one or moreampoules coupled to the HWCVD chamber and containing one or morechemical precursors to a temperature of about 25 to about 200 degreesCelsius; drawing a vapor of the one or more chemical precursors from theone or more ampoules using a carrier gas; exposing the substrate in theHWCVD chamber to one or more chemical precursors to deposit aself-assembled monolayer atop the copper surface, wherein the substrateis heated to a temperature of about 25 to about 350 degrees Celsius;wherein a pressure in the HWCVD chamber during deposition of theself-assembled monolayer is about 80 mTorr to about 500 Torr, andwherein the substrate is exposed to the one or more precursors for about30 to about 600 seconds; and depositing a second layer atop thesubstrate.

In some embodiments, a computer readable medium, having instructionsstored thereon which, when executed, cause a process chamber to performa method for processing a substrate having an exposed copper surface andan exposed silicon-containing surface. The method may include any of theembodiments disclosed herein.

Other and further embodiments of the present disclosure are describedbelow.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the present disclosure, briefly summarized above anddiscussed in greater detail below, can be understood by reference to theillustrative embodiments of the disclosure depicted in the appendeddrawings. However, the appended drawings illustrate only typicalembodiments of the disclosure and are therefore not to be consideredlimiting of scope, for the disclosure may admit to other equallyeffective embodiments.

FIG. 1 depicts an apparatus for coupling a hot wire source to a processchamber in accordance with some embodiments of the present disclosure.

FIG. 2 depicts a portion of an apparatus for coupling a hot wire sourceto a process chamber in accordance with some embodiments of the presentdisclosure.

FIG. 3 depicts a portion of an apparatus for coupling a hot wire sourceto a process chamber in accordance with some embodiments of the presentdisclosure.

FIG. 3A depicts a detail of the apparatus depicted in FIG. 3 inaccordance with some embodiments of the present disclosure.

FIG. 4 depicts a process chamber suitable for use with an apparatus forcoupling a hot wire source to a process chamber in accordance with someembodiments of the present disclosure.

FIG. 5 depicts a flow chart of a method for processing a substrate inaccordance with some embodiments of the present disclosure.

FIGS. 6A-G depict the stages of processing a substrate in accordancewith some embodiments of the present disclosure.

FIGS. 7A-G depict the stages of processing a substrate in accordancewith some embodiments of the present disclosure.

To facilitate understanding, identical reference numerals have beenused, where possible, to designate identical elements that are common tothe figures. The figures are not drawn to scale and may be simplifiedfor clarity. Elements and features of one embodiment may be beneficiallyincorporated in other embodiments without further recitation.

DETAILED DESCRIPTION

Methods and apparatus for improved in-situ cleaning of copper surfaceswithin a hot-wire chemical vapor deposition (HWCVD) chamber anddeposition and removal of self-assembled monolayers within the sameHWCVD chamber are provided herein. The inventive methods mayadvantageously provide methods of cleaning a copper surface (e.g.,removal of surface contaminants, oxide layers, or the like) andsubsequently depositing and removing of additional layers (e.g.,self-assembled monolayers, dielectric layers, UV Blok (barrier low k)layers, etc.) within the same process chamber that is more efficient andless time consuming than conventional substrate cleaning and depositionprocesses.

FIG. 5 is a flow diagram of a method 500 processing a substrate havingan exposed copper surface and an exposed silicon-containing surface inaccordance with some embodiments of the present disclosure. FIGS. 6A-6Gand 7A-7F are illustrative cross-sectional views of the substrate duringdifferent stages of the processing sequence of FIG. 5 in accordance withsome embodiments of the present disclosure. The inventive methods may beperformed in any HWCVD chamber suitable for processing semiconductorsubstrates in accordance with embodiments of the present disclosure,such as the HWCVD chamber discussed below with respect to FIGS. 1-4.

The method 500 generally begins at 502 by providing a substrate having acontaminant material disposed on the copper surface to a substratesupport within a hot wire chemical vapor deposition (HWCVD) chamber. Insome embodiments, the substrate may be a semiconductor wafer, such as a200 or 300 mm semiconductor wafer. Other size and geometry substratesmay also be used.

In some embodiments, as depicted in FIG. 6A, the substrate 600 comprisesan exposed copper surface 602 and an exposed silicon-containing surface604. In some embodiments, as depicted in FIG. 7A, the substrate 600comprises a barrier layer 702, for example tantalum or tantalum nitride,disposed atop the substrate 600 and an exposed copper surface 602 atopthe barrier layer 702.

The substrate 600 comprises a contaminant material 606 disposed on thecopper surface 602. In some embodiments, the contaminant material 606 tobe removed may form a layer on the copper surface 602. In someembodiments, the contaminant material 606 may also be present on thesilicon-containing surface 604. The contaminant material 606 may be anytype of material requiring removal. For example, in some embodiments,the contaminant material 606 formed on the copper surface 602 maycomprise oxygen, for example an oxide layer such as surface oxide ornative oxide layer comprising Cu(OH)₂, CuO, Cu₂O, and CuCO₃. Forexample, in some embodiments, the contaminant material 606 formed on thesilicon-containing surface 604 may comprise oxygen, for example an oxidelayer such as surface oxide or native oxide layer comprising siliconoxide. The contaminant material 606 may have a thickness of, for exampleabout 0.5 nm to about 20 nm nanometers.

Next, at 504, a hydrogen (H₂) gas may be provided to the HWCVD chamber.The hydrogen (H₂) gas may be provided to the HWCVD chamber at anysuitable flow rate, for example such as about 100 to about 700 sccm (forexample, for a 300 mm wafer process chamber). The flow rates providedherein may vary depending upon the size of the substrate being cleanedand/or of the processing volume of the HWCVD chamber. In someembodiments, the hydrogen (H₂) gas may be diluted, for example, with aninert gas such as helium (He), argon (Ar), or the like. In someembodiments, for example, the hydrogen (H₂) gas may be diluted withabout 5% to about 10% inert gas by volume. The amount of inert gas byvolume may be adjusted to provide an amount of hydrogen (H₂) necessaryto produce a needed amount of energy (when dissociated) to facilitateremoval of the contaminant material 606.

In embodiments where the hydrogen (H₂) gas is diluted, the hydrogen (H₂)gas and inert gas may be mixed prior to providing the gases to the HWCVDchamber. Alternatively, in some embodiments, the hydrogen (H₂) gas andinert gas may be co-flowed into the HWCVD chamber via two independentgas supplies and mixed within the HWCVD chamber.

Next at 506, the one or more filaments disposed in the HWCVD chamber areheated to a temperature sufficient to dissociate the hydrogen (H₂) gas.The one or more filaments may be any type of filaments, for example theone or more filaments may be composed of tantalum, tungsten, or iridium.In some embodiments, the one or more filaments may be any number offilaments suitable to cause dissociation of the hydrogen (H₂) gas, forexample 20 to 32 filaments. The one or more filaments may be heated toany temperature suitable to cause dissociation of the hydrogen (H₂) gasand, further, to provide a suitable amount of energy needed to removethe contaminant material 606, for example, such as about 1000 to about2400 degrees Celsius, more precisely about 1400 to about 1900 degreesCelsius. In some embodiments, the temperature may be at least in partdictated by the composition of the contaminant material 606 and, thus,the activation energy of a reaction between the dissociated gas and thecontaminant material 606 and/or the amount of energy needed to break thechemical bonds of the contaminant material 606 compounds, thusfacilitating removal of the contaminant material 606. In someembodiments, the one or more filaments are coupled to a power sourcesuitable for heating the one or more filaments to the temperature rangedescribed above. In some embodiments, a suitable power source providesabout 35 V to about 50 V of power at about 85 to about 90 A to the oneor more filaments.

Next, at 508 and as depicted in FIG. 6B and FIG. 7B, the substrate 600is exposed to the dissociated hydrogen (H₂) gas 614 to remove at leastsome of the contaminant material 606 from the copper surface 602. Asdepicted in FIG. 6C and FIG. 7C, by exposing the substrate 600 to thedissociated hydrogen (H₂) gas 614, hydrogen atoms react with thematerial disposed on the surface of the substrate (such as thecontaminant material 606), thus facilitating removal of the contaminantmaterial 606, thus cleaning the copper surface 602 of the substrate 600.For example, in embodiments where the contaminant material 606 comprisesan oxide (e.g., a native oxide layer), the hydrogen atoms react with theoxide causing an oxide reduction and volatile products form, namelymolecules of elements or hydrides of the elements and/or lower oxides.

The substrate 600 may be exposed to dissociated hydrogen (H₂) gas 614for any amount of time suitable to facilitate removal of the contaminantmaterial 606 from the copper surface 602. For example, in someembodiments, the substrate 600 may be exposed to the dissociatedhydrogen (H₂) gas 614 for about 150 to about 900 seconds to remove thecontaminant material 606 from the copper-containing surface.

To facilitate removal of the contaminant material 606, the substrate 600may be positioned under a HWCVD source (e.g., the filaments or wiresdescribed below with respect to FIG. 1-4) such that the substrate 600 isexposed to the hydrogen gas and decomposed species thereof. Thesubstrate 600 may be positioned under the HWCVD source on a substratesupport (e.g., substrate support pedestal 408 described below withrespect to FIG. 4) in a static position or, in some embodiments,dynamically to facilitate cleaning as the substrate 600 passes under theHWCVD source.

In addition to the above, additional process parameters may be utilizedto facilitate removal of the contaminant material 606 from the substrate600 and may be dictated in at least part by the amount of energy neededto remove the contaminant material 606. For example, in someembodiments, the process chamber may be maintained at a pressure ofabout 100 Torr to about 500 Torr. The chamber pressures provided hereinmay vary depending upon the size of the substrate being cleaned and/orof the processing volume of the HWCVD chamber. In some embodiments, thesubstrate 600 may be heated to a temperature of about 50 to about 400degrees Celsius, more precisely about 50 to about 300 degrees Celsius,to facilitate removal of the contaminant material 606 from the substrate600. Alternatively, or in combination, in some embodiments, the physicalparameters of the HWCVD chamber (e.g., filament diameter, filament tofilament distance, or filament to substrate distance) may be adjusted tofacilitate removal of the contaminant material 606 from the substrate600.

In any of the above embodiments, any of the process parameters (e.g.,flow rate of hydrogen (H₂) gas, ratio of hydrogen gas (H₂) to inert gas,substrate temperature, filament temperature, additional processparameters, physical parameters of the HWCVD chamber, or the like) maybe adjusted with respect to each other to provide the amount of energyneeded to facilitate removal of the contaminant material 606, forexample such as the activation energy of a reaction between thedissociated gas and the contaminant material 606 and/or the amount ofenergy needed to break the chemical bonds of the contaminant material606 compounds, thus facilitating removal of the contaminant material606. The inventive methods described above at 504-508 advantageouslyutilize suitable chemistry to treat the contaminated copper surface toremove the contaminated material and provide semiconductor qualitycopper with an atomically flat surface.

Next, at 510, the flow of hydrogen gas to the process chamber is stoppedand the one or more filaments are allowed to cool to a temperature ofabout 30 degrees Celsius to about 45 degrees Celsius. For example, theone or more filaments may be allowed to cool for about 60 to about 200seconds.

Next, at 512 and as depicted in FIG. 6D-6E and FIG. 7D-7E, the substrate600 in the HWCVD chamber is exposed to one or more chemical precursors608 to deposit a self-assembled monolayer 610 atop the copper surface602. The self-assembled monolayer 610 comprises a plurality of organicmolecules which self-assemble on a copper surface to form theself-assembled monolayer 610. The self-assembled monolayer 610 may besuitable as a diffusion barrier layer, as depicted in FIGS. 7A-7F or asa sacrificial layer for subsequent dielectric deposition process asdepicted in FIGS. 6A-6G.

The one or more chemical precursors 608 used for forming theself-assembled monolayer 610 comprise a head group proximate to thesubstrate 600 and a terminal tail group away from the substrate 600.These head and tail groups are connected by an intermediate portionreferred as a chain. The head group is selected to be a chemical groupthat bonds to the copper surface 602 and that provides thermal stabilityabove about 300 degrees Celsius (i.e., a chemical group that will notdecompose below about 300 degrees Celsius). The head group of thechemical precursor 608 molecule may contain a sulfur-containing groupfor example a thiol group, such as methanethiol (CH₃SH), ethanethiol(C₂H₅SH), or butanethiol (C₄H₉SH), N-alkanethiols {CH₃(CH₂)_(n-1)SHwhere n is 8, 12, 16, 18, 20, 22, or 29, and CF₃ and CF₂ terminatedthiols, for example CF₃(CF₂)_(n)(CH₂)₁₁)SH and CF₃(CF₂)₉(CH₂)_(n)SH(where n is 2, 11, or 17), and (CF₃(CH₂)_(n)SH) where n is 9-15. In someembodiments, the head group may contain a nitrogen containing group, forexample an amine group such as (3-Aminopropyl)triethoxysilane (APTES),(3-Aminopropyl)trimethoxysilane (APTMS), 1,3 damino propane, Ethylenediamine, EDTA, or diethyl amine, methylamine. In some embodiments, thehead group may further comprise silanes, phosphonic acid terminatedgroups and derivatives of phosphonic acid, such as[12-(benzo[b]benzo[4,5]thieno[2,3-d]thiophen-2-yl)dodecyl)]phosphonicacid (BTBT-C 12-PA),N-(2,2,3,3,4,4,4-heptafluoro-butyl)-N′-(undecyl-11-phosphonic acid)perylene-3,4,9,10-tetracarboxylic bisimide PBIF-PA,N-(2,2,3,3,4,4,4-heptafluoro-butyl)-N′-(undecyl-11-phosphonic aciddiethyl ester) perylene-3,4,9,10-tetracarboxylic bisimide,12-cyclohexyldodecylphosphonic acid (CDPA), and4-cyclohexylbutylphosphonic acid (CBPA). The chemical interactionbetween the interfacial copper surface 602 and the head group of thechemical precursor 608 molecule immobilizes the copper and inhibitscopper ionization and diffusion. The terminal tail group is selected toprovide hydrophobicity, for example a contact angle of greater thanabout 100 degrees Celsius, more precisely about 110 to about 120degrees. In some embodiments, the tail group may be a functional groupsuch as an alkoxysilane group, such as Octadecyltrimethoxysilane(ODTMS), nonafluorohexyltrimethoxysilane (NFHTMS),1H,1H,2H,2H-Perfluorodecyltrichlorosilane (PFTS),Chlorodimethyloctadecylsilane (CDODS),(3-MERCAPTOPROPYL)METHYLDIMETHOXYSILANE, Octadecyltrimethoxysilane(OTMS) (CH₃(CH₂)₁₇Si(OCH₃)₃, (17-aminoheptadecyl)trimethoxysilane(H₂N(CH₂)₁₇Si(OCH₃)₃ (AHTMS) also can addButyltrichlorosilane (BTS)(Chloro silane), and (Trichlorosilyl)Tricosanoate (MTST) (H₃CO₂C(CH₂)₂₂SiCl₃).

The chain comprises linear or aromatic hydrocarbons, such as —CH₂, C₆H₅,C₆H₄, C₂H₅, or —CH₂CH₂CH₃. The impact of the chain on copper diffusionis improved by selecting chemical precursors 608 of suitable chainlengths. For example, longer chain analogues of organic molecules canbetter inhibit diffusion than chemical precursors 608 with shorterchains, assuming similar terminal groups. For example, the inventorshave observed that hydrocarbons having chain lengths of about 8angstroms or more are better at inhibiting diffusion than hydrocarbonshaving a smaller chain length, such as about 3 to about 5 angstroms. Insome embodiments, 3-mecaptopropyltrimethoxysilane [(HS(CH₂)₃Si(OCH₃)₃](MPTMS) and 11-mercaptoundecyltrimethoxysilane (MUTMS) areadvantageously used for inhibiting copper diffusion whileoctadecyltrichlorosilane [CH₃(CH₂)₁₇SiCl₃], oxydiphthalic acid (ODPA) isused as a sacrificial layer.

In selecting a suitable self-assembled monolayer 610, desirablecharacteristics include hydrophobicity (i.e. a water contact angle ofgreater than 100 degrees), thermal stability in order to reduce orprevent decomposition during subsequent dielectric deposition, and easeof removal of the self-assembled monolayer 610. In one embodiment,examples of suitable chemical precursors 608 used to form theself-assembled monolayer 610 atop the copper surface 602 include3-mecaptopropyltrimethoxysilane [(HS(CH₂)₃Si(OCH₃)₃] (MPTMS),11-mercaptoundecyltrimethoxysilane (MUTMS), octadecyltrichlorosilane[CH₃(CH₂)₁₇SiCl₃], oxydiphthalic acid (ODPA), Octadecyltrimethoxysilane(ODTMS), Nonafluorohexyltrimethoxysilane (NFHTMS),1H,1H,2H,2H-Perfluorodecyltrichlorosilane (PFTS),(3-Aminopropyl)triethoxysilane (APTES), or(3-Aminopropyl)trimethoxysilane (APTMS).

The one or more chemical precursors 608 are introduced to the processchamber by a vapor draw deposition process. In some embodiments, aliquid chemical precursor 608 a placed in an ampoule coupled to theprocess chamber (for example gas supply 462 coupled to process chamber402) and heated to a temperature suitable for forming a vapor of thechemical precursor 608, for example a temperature of about 45 degreesCelsius to about 200 degrees Celsius. The vapor from the chemicalprecursor 608 is drawn from the ampoule, using for example an inertcarrier gas (i.e. a carrier gas that does not chemically react with thechemical precursor vapor) such as nitrogen, argon or the like, anddelivered to the process chamber In some embodiments, the chemicalprecursor 608 is a solid precursor (e.g. ODPA orchlorodimethyloctadecylsilane (CDODS)) and is dissolved in a polarsolvent, such as IPA, THF, DMSO, DMF, acetonitrile, nitromethane,dichloromethane, propylene carbonate, or the like, prior to heating thesolution in the ampoule as described above. In such embodiments, thesolvent evaporates in the bubbler and the vapor of the chemicalprecursor is delivered to the process chamber.

The process conditions to deposit these layers on a copper surface varyand mostly depend on the vapor pressure and stability of these moleculessubjected to thermal energy. In some embodiments, process parametersutilized in depositing a self-assembled monolayer 610 atop the coppersurface include a chamber temperature of about 45 degrees Celsius toabout 65 degrees Celsius, a substrate temperature of about 25 to about350 degrees Celsius, a chamber pressure of about 75 mTorr to about 500Torr. In some embodiments, the substrate is exposed to the chemicalprecursors 608 for a sufficient amount of time to form a self-assembledmonolayer 610 having a suitable thickness. For example in someembodiments, the substrate is exposed to the chemical precursors 608 forabout 30 seconds to about 900 seconds. In some embodiments, for examplewhere the self-assembled monolayer 610 is utilized as a copper barrierlayer, the thickness of self-assembled monolayer 610 is about 8angstroms to about 16 angstroms in order to optimize device performance.The thickness of the self-assembled monolayer 610 depends on the chainlength of the precursor molecule. As described above, chemicalprecursors 608 having longer chain lengths, and thus forming a thickerself-assembled monolayer 610, provide improved performance of theself-assembled monolayer 610 as a barrier layer as well as a sacrificiallayer. The inventors have observed that self-assembled monolayers 610formed from chemical precursors 608 having longer chain lengths are ableto provide improved coverage of the substrate surface and improvedability to withstand subsequent deposition conditions, for example forBlok/Black Diamond material deposition and for dielectric materialdeposition. The inventors have observed that optimization of the processconditions described above, which can vary depending on the chemicalprecursor, can advantageously form a self-assembled monolayer 610 havinga thickness as described above. In some embodiments, for example wherethe chemical precursor 608 is MPTMS, the chemical precursor 608 isheated in a bubbler at 65 degrees Celsius and the chemical precursorvapor is provided to the HWCVD process chamber via delivery lines heatedto about 75 degrees Celsius to prevent condensation. The HWCVD chamberwalls are maintained at about 65 degrees Celsius. The substrate isexposed to the chemical precursor vapor for about 180 seconds at achamber pressure of about 80 mTorr and a substrate temperature of about25 to about 85 degrees Celsius.

In some embodiments, at 514, and as depicted in FIG. 6F and FIG. 7F,after depositing the self-assembled monolayer 610, a second layer 612 isdeposited atop the substrate 600 in the HWCVD chamber. In someembodiments, the self-assembled monolayer 610 may be suitable as adiffusion barrier layer, as depicted in FIGS. 7A-7F. In suchembodiments, the second layer 612 is a UV Blok layer. The inventors haveobserved that depositing the self-assembled monolayer 610 as a copperbarrier layer allows the UV Block layer, typically about 100 angstroms,to be thinner, for example about 50 angstroms, thus advantageouslyreducing fabrication costs and processing time. In some embodiments, theself-assembled monolayer 610 may be suitable as a sacrificial layer asdepicted in FIGS. 6A-6G. In such embodiments, the second layer 612 is adielectric layer. The presence of the self-assembled monolayer 610 layeron the copper surface 602 prevents dielectric deposition on the coppersurface due to the hydrophobic nature of the self-assembled monolayer610. Any suitable dielectric layer 612, such as one or more of hafniumoxide, (HfO₂), Al₂O₃, TiO₂, Ti doped SiO₂, silicon oxide (SiO₂), siliconnitride (SiN), silicon oxynitride (SiON), or tantalum oxide (Ta₂O₅) maydeposited in the same process chamber via a chemical deposition process.

Following deposition of the UV Blok layer in embodiments where theself-assembled monolayer 610 is utilized as a diffusion barrier layer,the method generally 500 ends and the substrate 600 may proceed forfurther processing In some embodiments, subsequent processes such asdeposition, etch, annealing, or the like may be performed to fabricate afinished device, such as a memory device as depicted in FIG. 7G having afeature 704 formed in additional layers 706 (e.g., one or more of metal,metal containing, dielectric or anti-reflective coating (ARC) layers).

Following deposition of the dielectric layer, the self-assembledmonolayer 610 utilized as a sacrificial layer is removed as describedbelow. While the self-assembled monolayer 610 may be removed by a wetetch process, the inventors have observed that such processes do notcompletely remove the self-assembled monolayer 610 and are difficult toemploy. In contrast, the inventors have observed that removing theself-assembled monolayer 610 as described below advantageously removesthe self-assembled monolayer 610 completely.

To remove the self-assembled monolayer 610 hydrogen (H₂) gas is providedto the HWCVD chamber. The hydrogen (H₂) gas may be provided to the HWCVDchamber at any suitable flow rate, for example such as about 100 sccm toabout 400 sccm (for example, for a 300 mm wafer process chamber). Theflow rates provided herein may vary depending upon the size of thesubstrate being cleaned and/or of the processing volume of the HWCVDchamber. In some embodiments, the hydrogen (H₂) gas may be diluted, forexample, with an inert gas such as helium (He), argon (Ar), or the like.In some embodiments, for example, the hydrogen (H₂) gas may be dilutedwith about 5% to about 10% inert gas by volume. The amount of inert gasby volume may be adjusted to provide an amount of hydrogen (H₂)necessary to produce a needed amount of energy (when dissociated) tofacilitate removal of the self-assembled monolayer 610. In embodimentswhere the hydrogen (H₂) gas is diluted, the hydrogen (H₂) gas and inertgas may be mixed prior to providing the gases to the HWCVD chamber.Alternatively, in some embodiments, the hydrogen (H₂) gas and inert gasmay be co-flowed into the HWCVD chamber via two independent gas suppliesand mixed within the HWCVD chamber.

Next, the one or more filaments disposed in the HWCVD chamber are heatedto a temperature sufficient to dissociate the hydrogen (H2) gas. Thetemperature may be any temperature suitable to cause dissociation of thehydrogen (H₂) gas and, further, to provide a suitable amount of energyneeded to remove the self-assembled monolayer 610, for example, such asabout 1000 to about 2400 degrees Celsius, more precisely about 1400 toabout 1900 degrees Celsius. In some embodiments, the temperature may beat least in part dictated by the composition of the self-assembledmonolayer 610 and, thus, the activation energy of a reaction between thedissociated gas and the self-assembled monolayer 610 and/or the amountof energy needed to break the chemical bonds of the self-assembledmonolayer 610, thus facilitating removal of the self-assembled monolayer610.

Next, and as depicted in FIG. 6G, the substrate 600 is exposed to thedissociated hydrogen (H₂) gas 614 to remove the self-assembled monolayer610 from the copper surface 602. By exposing the substrate 600 to thedissociated hydrogen (H₂) gas 614, hydrogen atoms react with theself-assembled monolayer 610 molecules, comprising for example carbon,nitrogen, oxygen, sulfur and silicon, thus facilitating removal of theself-assembled monolayer 610 in the form of carbon dioxide, gaseoushydrogen, and water vapor.

The substrate 600 may be exposed to dissociated hydrogen (H₂) gas 614for any amount of time suitable to facilitate removal of theself-assembled monolayer 610. For example, in some embodiments, thesubstrate may be exposed to the dissociated hydrogen (H₂) gas 614 forabout 10 to about 600 seconds, more precisely from about 10 to about 300seconds.

To facilitate removal of the self-assembled monolayer 610 the substrate600 may be positioned under a HWCVD source (e.g., the filaments or wiresdescribed below with respect to FIG. 1-4) such that the substrate 600 isexposed to the hydrogen gas and decomposed species thereof. Thesubstrate 600 may be positioned under the HWCVD source on a substratesupport (e.g., substrate support pedestal 408 described below withrespect to FIG. 4) in a static position or, in some embodiments,dynamically to facilitate cleaning as the substrate 600 passes under theHWCVD source.

In addition to the above, additional process parameters may be utilizedto facilitate removal of the self-assembled monolayer 610 from thesubstrate 600 and may be dictated in at least part by the amount ofenergy needed to remove the self-assembled monolayer 610. For example,in some embodiments, the process chamber may be maintained at a pressureof about 80 mTorr to about 400 Torr. The chamber pressures providedherein may vary depending upon the size of the substrate being cleanedand/or of the processing volume of the HWCVD chamber. Alternatively, orin combination, in some embodiments, the physical parameters of theHWCVD chamber (e.g., filament diameter, filament to filament distance,or filament to substrate distance) may be adjusted to facilitate removalof the self-assembled monolayer 610 from the substrate 600.

In any of the above embodiments, any of the process parameters (e.g.,flow rate of hydrogen (H₂) gas, ratio of hydrogen gas (H₂) to inert gas,substrate temperature, filament temperature, additional processparameters, physical parameters of the HWCVD chamber, or the like) maybe adjusted with respect to each other to provide the amount of energyneeded to facilitate removal of the self-assembled monolayer 610, forexample such as the activation energy of a reaction between thedissociated gas and the self-assembled monolayer 610 and/or the amountof energy needed to break the chemical bonds of the self-assembledmonolayer 610, thus facilitating removal of the self-assembled monolayer610.

Furthermore, the inventors have observed that typically cleaning thecontaminant material 606 from a substrate, depositing a self-assembledmonolayer 610, depositing a subsequent dielectric layer, and removal ofthe self-assembled monolayer 610 are performed in multiple individualprocess chambers or in a cluster tool comprising multiple chambers, thusrequiring a transfer of substrates. In contrast, the inventors haveobserved that the method 500 may be performed within a single processchamber, such as the HWCVD process chamber described below in FIGS. 1-4to advantageously improve process efficiency and wafer throughput.

FIGS. 1-4 depict a hot wire chemical vapor deposition chamber suitableto perform the method 500 described above. Referring to FIG. 1, theapparatus 100 generally includes a housing 102 having a filamentassembly (hot wire source) 106 configured to be disposed within thehousing 102. The housing 102 is configured to fit within and/or becoupled to a process chamber. For example, the housing 102 may beconfigured to be coupled between a chamber body and a chamber lid, suchas in the process chamber described below with respect to FIG. 4. Insome embodiments, the housing 102 generally comprises a top 124, abottom 126, opposing sides 132, 144 coupling the top 124 to the bottom126, a first open end 128 and an opposing second end 130 opposing thefirst open end. The second end 130 may be an open end as well. A recess107 is formed in the housing between the first open end 128 and thesecond end 130 to fit the filament assembly 106 within the recess 107. Athrough hole 104 is formed through the top 124 and bottom 126 of thehousing 102 to expose a portion of the filament assembly 106. Thehousing 102 may be fabricated from any suitable process compatiblematerial, for example, a metal such as aluminum, stainless steel, or thelike.

In some embodiments, the top 124 and bottom 126 are configured to couplethe housing 102 to, or to interface with, the process chamber (e.g., thebottom 126 to a chamber body and the top 124 to a chamber lid, asdepicted in FIG. 4) and may comprise one or more features to facilitatesuch coupling or interfacing. For example, in some embodiments, one ormore pins (three pins 122 shown) may be coupled to and, protrude from,the top 124 of the housing 102. When present, the one or more pins areconfigured to interface with features of the process chamber to providea predetermined alignment of the housing 102 with respect to the processchamber. In some embodiments, the bottom 126 may include one or morepins (not shown) that function similar to the one or more pins of thetop 124. Alternatively, the bottom 126 may include one or more openings(openings 123 shown in phantom) that can mate with one or more pinsextending from the chamber body.

The through hole 104 exposes the filaments (shown in FIGS. 3-3A) of thefilament assembly 106 to allow a process gas to be provided to thefilaments and a resultant process resource (e.g., a dissociated gas)formed by an interaction of the process gas and the filaments to beprovided to an inner volume of the process chamber to facilitateperforming a process. In some embodiments, the through hole 104 may havedimensions suitable to expose a predetermined amount of filaments and,in some embodiments, may be dependent on a size of a gas distributionmechanism (e.g., showerhead, nozzles of the like) within the processchamber, an inner volume of the process chamber, or a size of asubstrate being processed. In some embodiments, a channel 138 may beformed about the through hole 104 to accommodate an o-ring to facilitateforming an air tight seal between the housing 102 and process chamberwhen the housing 102 is coupled to the process chamber. In someembodiments, a liner 108 may be disposed on an inner surface of thethrough hole 104. When present, the liner 108 may protect exposedportions of the housing 102 during processing. The liner 108 may befabricated from any suitable process compatible material, for example,aluminum, alumina (Al2O3), stainless steel, or the like. Although shownon just the top 124 of the housing 102, either or both of the channel138 and liner 108 may also be provided on the bottom 126 of the housing102.

In some embodiments, a first cover plate 110 and a second cover plate112 may be coupled to the housing 102, to cover the first open end 128and second end 130, respectively. The first cover plate 110 and thesecond cover plate 112 may be coupled to the housing 102 via a pluralityof fasteners 134, 136. In some embodiments, the first cover plate 110may comprise one or more electrical feedthroughs disposed through thefirst cover plate 110 to facilitate providing electrical power to thefilament assembly 106. For example, in some embodiments, a firstelectrical feedthrough 114 may be disposed through the first cover plate110 to facilitate providing power to the filament assembly 106 (viaconductor 115 during use) and a second electrical feedthrough 116 may bedisposed through the first cover plate 110 to provide a return path (viaconductor 117) for the power provided via the first electricalfeedthrough 114.

In some embodiments, one or more gas holes (two gas holes 118, 120shown) may be disposed in the top 124 of the housing 102 to interfacewith gas inputs of the process chamber (such as chamber lid) to allow aflow of a process gas through the housing 102 to a gas distributionmechanism (e.g., a showerhead, nozzle, or the like) of the chamber lidwhen the apparatus is coupled to the process chamber. The one or moregas holes 118, 120 are fluidly coupled to respective gas holes (notshown) disposed in the bottom 126 of the housing 102 via respectiveconduits 140, 142 (partially shown in phantom) formed in the housing102. The conduits 140, 142 provide a flow path from the gas holes in thebottom 126 to the gas holes 118, 120 in the top 124 such that the gasholes in the top 124 and the bottom 126 are positioned to align withrespective gas holes in a chamber body and a chamber lid to which thehousing will be attached (as discussed below with respect to FIG. 4)even when a straight line path is not available (for example due to theopening at the first open end 128). In some embodiments, each gas holein the top 124 and bottom 126 may include a groove formed around the gashole to accommodate an o-ring to provide a vacuum seal with componentsof the process chamber (e.g., a gas conduit) when the housing 102 iscoupled to the process chamber.

Referring to FIG. 2, in some embodiments, the housing 102 may include aplurality of features 212, 214, 216, 218, (e.g., extensions, cutouts orthe like) to interface or with surfaces or features of the processchamber. For example, the housing 102 may have a peripheral geometrythat is similar to or identical to the process chamber geometry at theinterface of the chamber body and the chamber lid, such that the housing102 may be interposed between the chamber body and the chamber lid. Thebottom 126 of the housing 102 maintains all critical features foralignment, fluid coupling, or the like, as the chamber lid. Similarly,the top 124 of the housing 102 maintains all critical features foralignment, fluid coupling, or the like, as the chamber body. As such,the chamber lid may be coupled to the housing 102 just as the chamberlid would be coupled to the chamber body and the chamber body may becoupled to the housing 102 just as the chamber body would be coupled tothe chamber lid.

The first open end 128 is sized to allow the filament assembly (106 inFIG. 1) to be inserted into the housing 102 through the first open end128. In some embodiments, a groove 210 may be formed about the firstopen end 128 to accommodate an o-ring to provide an air tight sealbetween the first cover plate (110 in FIG. 1) and the housing 102 whenthe first cover plate 110 is coupled to the housing. In someembodiments, one or more pins (two pins 224, 226 shown) may be disposedabout the first open end 128, the pins 224, 226 configured to interfacewith holes formed in the first cover plate 110 to provide alignment ofthe first cover plate 110 and the housing 102 when the first cover plate110 is coupled to the housing 102. In some embodiments, a similar groove(not shown) and pins (not shown) may be disposed about the second openend (second end 130 in FIG. 1) that function similar to the groove 210and pins 224, 226 disposed about the first open end 128.

In some embodiments, one or more holes 220, 222 may be formed in thebottom 126 of the housing 102 within the first open end 128 to receive afastener to facilitate securing the filament assembly 106 within thehousing 102. In some embodiments, the holes 220, 222 may be threaded tointerface with mating threads of the fasteners.

Referring to FIG. 3, in some embodiments, the filament assembly (hotwire source) 106 generally comprises a frame 302, a top 348 and bottom340. The frame 302 may be fabricated from any suitable processcompatible material, for example, a metal such as aluminum, stainlesssteel, or the like.

The top 348 and bottom 340 cover at least a portion of the frame 302and, in some embodiments, provide additional structural support to theframe 302. The top 348 and bottom 340 may be coupled to the frame 302via, for example, a plurality of fasteners 354. A through hole 342 isdisposed through each of the top 348 and bottom 340 to form an opening343 that corresponds with the opening defined by the through hole 104 inthe top 124 and bottom 126 of the housing 102 (described above).

The frame 302 is generally rectangular in shape and sized to fit withinthe first open end (128 in FIGS. 1 and 2) to allow the filament assembly106 to be inserted into the housing 102. Providing a frame 302 that isremovable from the housing assembly allows for the filament assembly 106to be easily removed and repaired (for example to replace a brokenfilament) or replaced with, for example, a different filament assembly106 having the same or a different filament configuration to facilitateperforming a predetermined process without removing the chamber lid. Theframe 302 generally comprises a first end 310, a second end 312 andsides 304, 306 coupling the first end 310 to the second end 312.

In some embodiments, each of the first end 310 and second end 312comprise a plurality of connectors 314, 316 configured to hold theplurality of filaments 308 within the frame 302 at a predeterminedspacing and/or a predetermined tension and to provide electrical contactto the plurality of filaments 308. In some embodiments, a set of theplurality of connectors (e.g., the connectors 316 of the second end 312)may comprise springs 352 to exert a tension on the plurality offilaments 308 to prevent the filaments from sagging during processing,for example such as shown in FIG. 3A. In some embodiments, a tension ofthe filament 308 may be adjustable via either or both of the connectors314, 316. Referring back to FIG. 3, in some embodiments, each of thefirst end 310 and second end 312 comprise a plurality of through holes344, 346 to allow the plurality of filaments 308 to pass through thefirst end 310 and second end 312 to the connectors 314, 316. In suchembodiments, each of the through holes 344, 346 may have a diametersufficient to prevent contact with the filament and may optionallyinclude an electrically insulating material disposed within each of thethrough holes 344, 346 to facilitate electrically isolating theplurality of filaments 308 from the first end 310 and second end 312.

In some embodiments, each of the first end 310 and the second end 312comprises a plurality of tabs 322, 324, 334, 336 configured tocorrespond with the holes 220, 222 formed in the housing 102 tofacilitate securing the filament assembly 106 within the housing 102. Insome embodiments, each of the first end 310 and second end 312 may havean outer member 328, 356 to couple the first end 310 and the second end312 to the frame 302. The outer member 328, 356 includes a plurality ofthrough holes 357 to receive fasteners to couple the first end 310 andsecond end 312 to the sides 304, 306.

In some embodiments, the first end 310 comprises a first electricalcoupling 318 and a second electrical coupling 320 to interface with thefirst electrical feedthrough 114 and second electrical feedthrough 116of the housing 102 (described above) to facilitate providing electricalpower to the plurality of filaments 308. In such embodiments, the firstelectrical feedthrough 114 and second electrical feedthrough 116 areelectrically coupled to the plurality of filaments 308 to facilitateproviding power to the plurality of filaments 308.

Power may be provided to the plurality of filaments 308 as a group(e.g., in a single zone), or in multiple zones each comprising one ormore filaments 308. For example, in some embodiments, the one or morefilaments 308 may be configured in a single zone. In such embodiments,the one or more filaments 308 may be electrically coupled to one anotherin parallel and provided power from a single power source.Alternatively, in some embodiments, the one or more filaments 308 may beconfigured in a plurality of zones. The one or more filaments 308 may beconfigured in any number of zones, for example such as two zones orthree zones. In some embodiments, each zone of the plurality of zonesmay be coupled have a separate power source to allow for independentadjustment of each zone of the plurality of zones. Examples of suchzoned configurations that may be used in combination with the one ormore filaments 308 described herein is disclosed in greater detail inU.S. patent application Ser. No. 13/723,409, filed Dec. 21, 2012,entitled, “Methods and Apparatus for Cleaning Substrate Surfaces withHydrogen”.

Although only two filaments of the plurality of filaments 308 are shownin FIG. 3, the plurality of filaments 308 may include any number offilaments sufficient to cover a predetermined area within the frame 302.In some embodiments, the plurality of filaments (wires) 308 may beseparate wires, or may be a single wire routed back and forth across theframe 302. The plurality of filaments 308 may comprise any suitableconductive material, for example, such tungsten, tantalum, iridium,nickel-chrome, palladium, or the like. The plurality of filaments 308may have any thickness, geometry and/or density suitable to facilitate apredetermined process in the process chamber, and may be dependent on,for example, a substrate composition, materials and/or process gasesutilized in the process and the dimensions of the process chamber. Insome embodiments, a distance between each filament of the plurality offilaments 308 (i.e., the wire to wire distance) may be varied inaccordance with a particular application.

FIG. 4 depicts a system 400 suitable for processing a substrate inaccordance with some embodiments of the present disclosure. The system400 may comprise a controller 450 and a process chamber 402 having anexhaust system 420 for removing excess process gases, processingby-products, or the like, from the interior of the process chamber 402.Exemplary process chambers may include chemical vapor deposition (CVD)or other process chambers, available from Applied Materials, Inc. ofSanta Clara, Calif. Other suitable process chambers may similarly beused.

The process chamber 402 has a chamber body 404 and a chamber lid 406generally enclosing a processing volume 405. The processing volume 405may be defined, for example, between a substrate support pedestal 408disposed within the process chamber 402 for supporting a substrate 410thereupon during processing and one or more gas inlets, such as ashowerhead 414 coupled to the chamber lid 406 and/or nozzles provided atpredetermined locations. In some embodiments, the inventive apparatus100 may be coupled to the process chamber 402 disposed between thechamber body 404 and the chamber lid 406. In such embodiments, one ormore process gases may be provided to the filaments 308 of the filamentassembly (hot wire source) 106 via the showerhead 414 to facilitate aprocess within the processing volume 405. A power supply 460 (e.g., a DCpower supply) is coupled to the apparatus 100 to provide power to thefilaments 308.

In some embodiments, the substrate support pedestal 408 may include amechanism that retains or supports the substrate 410 on the surface ofthe substrate support pedestal 408, such as an electrostatic chuck, avacuum chuck, a substrate retaining clamp, or the like (not shown). Insome embodiments, the substrate support pedestal 408 may includemechanisms for controlling the substrate temperature (such as heatingand/or cooling devices, not shown) and/or for controlling the speciesflux and/or ion energy proximate the substrate surface.

For example, in some embodiments, the substrate support pedestal 408 mayinclude an RF bias electrode 440. The RF bias electrode 440 may becoupled to one or more bias power sources (one bias power source 438shown) through one or more respective matching networks (matchingnetwork 436 shown). The one or more bias power sources may be capable ofproducing up to 12,000 W at a frequency of about 2 MHz, or about 13.56MHz, or about 60 Mhz. In some embodiments, two bias power sources may beprovided for coupling RF power through respective matching networks tothe RF bias electrode 440 at respective frequencies of about 2 MHz andabout 13.56 MHz. In some embodiments, three bias power sources may beprovided for coupling RF power through respective matching networks tothe RF bias electrode 440 at respective frequencies of about 2 MHz,about 13.56 MHz, and about 60 Mhz. The at least one bias power sourcemay provide either continuous or pulsed power. In some embodiments, thebias power source alternatively may be a DC or pulsed DC source.

The substrate 410 may enter the process chamber 402 via an opening 412in a wall of the process chamber 402. The opening 412 may be selectivelysealed via a slit valve 418, or other mechanism for selectivelyproviding access to the interior of the chamber through the opening 412.The substrate support pedestal 408 may be coupled to a lift mechanism434 that may control the position of the substrate support pedestal 408between a lower position (as shown) suitable for transferring substratesinto and out of the chamber via the opening 412 and a selectable upperposition suitable for processing. The process position may be selectedto maximize process uniformity for a particular process. When in atleast one of the elevated processing positions, the substrate supportpedestal 408 may be disposed above the opening 412 to provide asymmetrical processing region.

A gas supply 462 may be coupled to the apparatus 100 and/or showerhead414 to provide one or more process gases to the apparatus 100 and/orshowerhead 414 for processing. For example, the gas supply 462 may becoupled to the chamber body 404 with the provided gas traveling throughthe chamber body 404, through the housing 102 (e.g., via conduits 140),and through the chamber lid 406 to the showerhead 414. Alternatively,the gas supply 462 may be coupled directly to the showerhead, as shownin phantom. The apparatus 100 may advantageously be configured tointerface with the process chamber 402. Although a showerhead 414 isshown in FIG. 4, additional or alternative gas inlets may be providedsuch as nozzles or inlets disposed in the ceiling or on the sidewalls ofthe process chamber 402 or at other locations suitable for providinggases to the process chamber 402, such as the base of the processchamber, the periphery of the substrate support pedestal, or the like.

The exhaust system 420 generally includes a pumping plenum 424 and oneor more conduits that couple the pumping plenum 424 to the inner volume(and generally, the processing volume 405) of the process chamber 402,for example via one or more inlets 422 (two inlets shown in FIG. 4). Avacuum pump 428 may be coupled to the pumping plenum 424 via a pumpingport 426 for pumping out the exhaust gases from the process chamber 402.The vacuum pump 428 may be fluidly coupled to an exhaust outlet 432 forrouting the exhaust as needed to appropriate exhaust handling equipment.A valve 430 (such as a gate valve, or the like) may be disposed in thepumping plenum 424 to facilitate control of the flow rate of the exhaustgases in combination with the operation of the vacuum pump 428. Althougha z-motion gate valve is shown, any suitable, process compatible valvefor controlling the flow of the exhaust may be utilized.

To facilitate control of the process chamber 402 as described above, thecontroller 450 may be one of any form of general-purpose computerprocessor that can be used in an industrial setting for controllingvarious chambers and sub-processors. The memory, or computer-readablemedium, 456 of the CPU 452 may be one or more of readily availablememory such as random access memory (RAM), read only memory (ROM),floppy disk, hard disk, or any other form of digital storage, local orremote. The support circuits 454 are coupled to the CPU 452 forsupporting the processor in a conventional manner. These circuitsinclude cache, power supplies, clock circuits, input/output circuitryand subsystems, and the like.

Processes may generally be stored in the memory 456 as a softwareroutine 458 that, when executed by the CPU 452, causes the processchamber 402 to perform processes of the present disclosure. The softwareroutine 458 may also be stored and/or executed by a second CPU (notshown) that is remotely located from the hardware being controlled bythe CPU 452. Some or all of the method of the present disclosure mayalso be performed in hardware. As such, the process may be implementedin software and executed using a computer system, in hardware as, e.g.,an application specific integrated circuit or other type of hardwareimplementation, or as a combination of software and hardware. Thesoftware routine 458 may be executed after the substrate 410 ispositioned on the substrate support pedestal 408. The software routine458, when executed by the CPU 452, transforms the general purposecomputer into a specific purpose computer (controller) 450 that controlsthe chamber operation such that the processes are performed.

While the foregoing is directed to embodiments of the presentdisclosure, other and further embodiments of the disclosure may bedevised without departing from the basic scope thereof.

The invention claimed is:
 1. A method of processing a substrate havingan exposed copper surface, comprising: (a) providing a substrate havinga contaminant material disposed on the copper surface to a substratesupport within a hot wire chemical vapor deposition (HWCVD) chamber; (b)providing hydrogen (H₂) gas to the HWCVD chamber; (c) heating one ormore filaments disposed in the HWCVD chamber to a temperature sufficientto dissociate the hydrogen (H₂) gas; (d) exposing the substrate to thedissociated hydrogen (H₂) gas to remove at least some of the contaminantmaterial from the copper surface; (e) cooling the one or more filamentsto room temperature; (f) exposing the substrate in the HWCVD chamber toone or more chemical precursors to deposit a self-assembled monolayeratop the copper surface; and (g) depositing a second layer atop thesubstrate.
 2. The method of claim 1, wherein depositing the second layerfurther comprises: after depositing the self-assembled monolayer,selectively depositing a dielectric layer atop an exposedsilicon-containing surface of the substrate in the HWCVD chamber;providing hydrogen (H₂) gas to the HWCVD chamber; heating the one ormore filaments disposed in the HWCVD chamber to a temperature sufficientto dissociate the hydrogen (H₂) gas; and exposing the substrate to thedissociated hydrogen (H₂) gas to remove the self-assembled monolayerfrom the copper surface.
 3. The method of claim 2, wherein a temperatureof the substrate during removal of the self-assembled monolayer from thecopper surface is about 25 to about 350 degrees Celsius.
 4. The methodof claim 1, wherein depositing the second layer further comprises:depositing a UV Block layer atop the self-assembled monolayer.
 5. Themethod of claim 1, wherein the filament temperature is about 1000 toabout 2400 degrees Celsius.
 6. The method of claim 1, wherein the one ormore filaments comprise 20 to 32 filaments.
 7. The method of claim 1,wherein the one or more filaments are composed of tantalum, tungsten, oriridium.
 8. The method of claim 1, wherein during (b)-(d), the substratesupport is heated to about 50 to about 400 degrees Celsius.
 9. Themethod of claim 1, wherein the self-assembled monolayer has a thicknessof about 12 to about 13 angstroms.
 10. The method of claim 1, whereinthe one or more chemical precursors comprise at least one of3-mecaptopropyltrimethoxysilane, 11-mercaptoundecyltrimethoxysilane,octadecyltrimethoxysilane (ODTMS), nonafluorohexylmethyltrimethoxysilane(NFHTMS), 1H,1H,2H,2H-perfluorodecyltrichlorosilane (PFTS),(3-aminopropyl)triethoxysilane(APTES),(3-aminopropyl)trimethoxysilane(APTMS), octadecyltrichlorosilane,oxydiphthalic acid (ODPA), chlorodimethyloctadecylsilane (CDODS),(3-mercaptopropyl)methyldimethoxysilane, octadecyltrimethoxysilane(OTMS)(CH₃(CH₂)₁₇Si(OCH₃)₃, (17-aminoheptadecyl)trimethoxysilane(H₂N(CH₂)₁₇Si(OCH₃)₃ (AHTMS) butyltrichlorosilane(BTS)(Chloro silane), or (trichlorosilyl) tricosanoate (MTST)(H₃CO₂C(CH₂)₂₂SiCl₃).
 11. The method of claim 1, wherein exposing thesubstrate to one or more chemical precursors further comprises: heatingone or more ampoules containing one or more chemical precursors; anddrawing a vapor of the one or more chemical precursors from the one ormore ampoules using a carrier gas.
 12. The method of claim 11, furthercomprising heating the one or more ampoules to a temperature of about 45degrees Celsius to about 200 degrees Celsius.
 13. The method of claim 1,wherein a temperature of the substrate during deposition of theself-assembled monolayer is about 25 to about 350 degrees Celsius. 14.The method of claim 1, wherein a pressure in the HWCVD chamber duringdeposition of the self-assembled monolayer is about 80 mTorr to about500 Torr.
 15. The method of claim 1, wherein the substrate is exposed tothe one or more chemical precursors for about 30 seconds to about 600seconds.
 16. A method of processing a substrate having an exposed coppersurface, comprising: providing a substrate having a contaminant materialdisposed on the copper surface to a substrate support within a hot wirechemical vapor deposition (HWCVD) chamber; providing hydrogen (H₂) gasto the HWCVD chamber; heating one or more filaments disposed in theHWCVD chamber to a temperature of about 1000 to about 2400 degreesCelsius to dissociate the hydrogen (H₂) gas and heating the substratesupport to a temperature of about 50 to about 400 degrees Celsius;exposing the substrate to the dissociated hydrogen (H₂) gas to remove atleast some of the contaminant material from the copper surface; coolingthe one or more filaments to room temperature; heating one or moreampoules coupled to the HWCVD chamber and containing one or morechemical precursors to a temperature of about 25 to about 200 degreesCelsius; drawing a vapor of the one or more chemical precursors from theone or more ampoules using a carrier gas; exposing the substrate in theHWCVD chamber to one or more chemical precursors to deposit aself-assembled monolayer atop the copper surface, wherein the substrateis heated to a temperature of about 25 to about 350 degrees Celsius;wherein a pressure in the HWCVD chamber during deposition of theself-assembled monolayer is about 80 mTorr to about 500 Torr, andwherein the substrate is exposed to the one or more chemical precursorsfor about 30 to about 600 seconds; and depositing a second layer atopthe substrate.
 17. The method of claim 16, wherein depositing the secondlayer further comprises: after depositing the self-assembled monolayer,selectively depositing a dielectric layer atop an exposedsilicon-containing surface of the substrate in the HWCVD chamber;providing hydrogen (H₂) gas to the HWCVD chamber; heating the one ormore filaments disposed in the HWCVD chamber to a temperature sufficientto dissociate the hydrogen (H₂) gas; and exposing the substrate to thedissociated hydrogen (H₂) gas to remove the self-assembled monolayerfrom the copper surface, wherein a temperature of the substrate duringremoval of the self-assembled monolayer from the copper surface is about150 to about 350 degrees Celsius.
 18. The method of claim 16, whereindepositing the second layer further comprises: depositing a UV Blocklayer atop the self-assembled monolayer.
 19. A non-transitory computerreadable medium, having instructions stored thereon which, whenexecuted, cause a process chamber to perform a method of processing asubstrate having an exposed copper surface and an exposedsilicon-containing surface, the method comprising: (a) providing asubstrate having a contaminant material disposed on the copper surfaceto a substrate support within a hot wire chemical vapor deposition(HWCVD) chamber; (b) providing hydrogen (H₂) gas to the HWCVD chamber;(c) heating one or more filaments disposed in the HWCVD chamber to atemperature sufficient to dissociate the hydrogen (H₂) gas; (d) exposingthe substrate to the dissociated hydrogen (H₂) gas to remove at leastsome of the contaminant material from the copper surface; (e) coolingthe one or more filaments to room temperature; (f) exposing thesubstrate in the HWCVD chamber to one or more chemical precursors todeposit a self-assembled monolayer atop the copper surface; and (g)depositing a second layer atop the substrate.
 20. The non-transitorycomputer readable medium of claim 19, wherein depositing the secondlayer further comprises: after depositing the self-assembled monolayer,selectively depositing a dielectric layer atop the silicon-containingsurface of the substrate in the HWCVD chamber; providing hydrogen (H₂)gas to the HWCVD chamber; heating the one or more filaments disposed inthe HWCVD chamber to a temperature sufficient to dissociate the hydrogen(H₂) gas; and exposing the substrate to the dissociated hydrogen (H₂)gas to remove the self-assembled monolayer from the copper surface.